JP2001130956A - Piezoelectric ceramic composition and piezoelectric ceramic element by using the same - Google Patents
Piezoelectric ceramic composition and piezoelectric ceramic element by using the sameInfo
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- JP2001130956A JP2001130956A JP2000161832A JP2000161832A JP2001130956A JP 2001130956 A JP2001130956 A JP 2001130956A JP 2000161832 A JP2000161832 A JP 2000161832A JP 2000161832 A JP2000161832 A JP 2000161832A JP 2001130956 A JP2001130956 A JP 2001130956A
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- piezoelectric ceramic
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- 239000000919 ceramic Substances 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 230000008878 coupling Effects 0.000 abstract description 17
- 238000010168 coupling process Methods 0.000 abstract description 17
- 238000005859 coupling reaction Methods 0.000 abstract description 17
- 238000010304 firing Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は圧電磁器組成物お
よびそれを用いた圧電セラミック素子に関し、特にたと
えば、圧電セラミックフィルタ、圧電セラミック発振子
および圧電セラミック振動子などの圧電セラミック素子
などの材料として有用な圧電磁器組成物およびそれを用
いた圧電セラミック素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition and a piezoelectric ceramic element using the same, and is particularly useful as a material for a piezoelectric ceramic element such as a piezoelectric ceramic filter, a piezoelectric ceramic oscillator and a piezoelectric ceramic oscillator. The present invention relates to a piezoelectric ceramic composition and a piezoelectric ceramic element using the same.
【０００２】[0002]
【従来の技術】圧電セラミックフィルタ、圧電セラミッ
ク発振子および圧電セラミック振動子などの圧電セラミ
ック素子に用いられる圧電磁器組成物として、従来、チ
タン酸ジルコン酸鉛（Ｐｂ（Ｔｉx Ｚｒ1-x ）Ｏ3 ）ま
たはチタン酸鉛（ＰｂＴｉＯ3）を主成分とする圧電磁
器組成物が広く用いられている。しかしながら、チタン
酸ジルコン酸鉛またはチタン酸鉛を主成分とする圧電磁
器組成物では、その組成中に鉛を多量に含有するため、
製造過程において鉛酸化物の蒸発のため製品の均一性が
低下するという問題があった。製造過程における鉛酸化
物の蒸発による製品の均一性の低下を防止するために
は、組成中に鉛をまったく含まないまたは少量のみ含む
圧電磁器組成物が好ましい。これ対して、ＣａＢｉ4 Ｔ
ｉ4 Ｏ15などのビスマス層状化合物を主成分とする圧電
磁器組成物では、その組成中に鉛酸化物を含有しないた
め、上記のような問題は生じない。BACKGROUND ART piezoelectric ceramic filter, a piezoelectric ceramic composition used for the piezoelectric ceramic element such as a piezoelectric ceramic oscillator and a piezoelectric ceramic oscillator, conventionally, lead zirconate titanate (Pb (Ti x Zr 1- x) O Piezoelectric ceramic compositions containing 3 ) or lead titanate (PbTiO 3 ) as a main component are widely used. However, a piezoelectric ceramic composition containing lead zirconate titanate or lead titanate as a main component contains a large amount of lead in the composition,
In the manufacturing process, there is a problem that the uniformity of the product is reduced due to evaporation of the lead oxide. A piezoelectric ceramic composition containing no or only a small amount of lead in its composition is preferred in order to prevent a reduction in product uniformity due to evaporation of lead oxides during the production process. In contrast, CaBi 4 T
The piezoelectric ceramic composition containing a bismuth layered compound such as i 4 O 15 as a main component does not contain a lead oxide in the composition, so that the above-described problem does not occur.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、ＣａＢ
ｉ4 Ｔｉ4 Ｏ15などを主成分とする圧電磁器組成物で
は、実用に供しうる程度の電気機械結合係数ｋｔ（１０
％以上）を示す圧電磁器を得るためには１１５０℃以上
の高温で焼成することが必要であり、このような高温で
の焼成が可能な高価な焼成炉が必要である。また、内部
電極を有する圧電セラミックフィルタなどの圧電セラミ
ック素子などでは、焼成温度より高い融点を有する電極
材料を用いなければならず、白金やパラジウムなどの高
価な電極材料を用いる必要があるため、製造コストが増
大するという問題があった。However, CaB
In a piezoelectric ceramic composition mainly composed of i 4 Ti 4 O 15 or the like, an electromechanical coupling coefficient kt (10
%) Is required to be fired at a high temperature of 1150 ° C. or more, and an expensive firing furnace capable of firing at such a high temperature is required. In addition, for a piezoelectric ceramic element such as a piezoelectric ceramic filter having an internal electrode, an electrode material having a melting point higher than the firing temperature must be used, and expensive electrode materials such as platinum and palladium must be used. There was a problem that cost increased.
【０００４】それゆえに、この発明の主たる目的は、Ｃ
ａＢｉ4 Ｔｉ4 Ｏ15を主成分とする圧電磁器組成物の焼
成が可能な温度を低下させ、１１００℃以下の焼成温度
で実用に供しうる程度の電気機械結合係数ｋｔを示す圧
電セラミックフィルタ、圧電セラミック発振子および圧
電セラミック振動子などの圧電セラミック素子などの材
料として有用な圧電磁器組成物およびそれを用いた圧電
セラミック素子を提供することである。[0004] Therefore, the main object of the present invention is to provide a C
a piezoelectric ceramic filter that reduces the temperature at which a piezoelectric ceramic composition containing aBi 4 Ti 4 O 15 as a main component can be fired and exhibits an electromechanical coupling coefficient kt at a firing temperature of 1100 ° C. or less, which is practically usable; An object of the present invention is to provide a piezoelectric ceramic composition useful as a material for a piezoelectric ceramic element such as a ceramic oscillator and a piezoelectric ceramic oscillator, and a piezoelectric ceramic element using the same.
【０００５】[0005]
【課題を解決するための手段】この発明にかかる圧電磁
器組成物は、一般式ＣａＢｉ4 Ｔｉ4 Ｏ15で表される主
成分からなる圧電磁器組成物において、少なくともＷを
その一般式で表される主成分中のＢｉ、１ｍｏｌに対し
て０．５ｍｏｌ以下（０を含まない）含有することを特
徴とする、圧電磁器組成物である。この場合、この発明
にかかる圧電磁器組成物は、たとえば一般式ＣａＢｉ4
（Ｔｉ1-y Ｗy ）4 Ｏ15（ただし、０＜ｙ≦０．５）で
表される主成分からなる。この発明にかかる圧電磁器組
成物では、Ｃａ以外の２価の金属元素がＢｉ、１ｍｏｌ
に対して０．１２５ｍｏｌ以下（０を含まない）含有さ
れてもよい。この場合、含有されるＣａ以外の２価の金
属元素は、たとえばＭｇ、ＳｒおよびＢａのうちの少な
くとも１種である。また、この発明にかかる圧電磁器組
成物では、Ｂｉ以外の３価の金属元素がＢｉ、１ｍｏｌ
に対して０．０７５ｍｏｌ以下（０を含まない）含有さ
れてもよい。この場合、含有されるＢｉ以外の３価の金
属元素は、たとえばＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇ
ｄ、Ｄｙ、Ｅｒ、Ｙｂ、ＳｃおよびＹのうちの少なくと
も１種である。さらに、この発明にかかる圧電磁器組成
物では、マンガンがＭｎＣＯ3 に換算して１．５重量％
以下（０を含まない）含有されてもよい。この発明にか
かる圧電セラミック素子は、この発明にかかる圧電磁器
組成物からなる圧電磁器と、圧電磁器に形成される電極
とを含む、圧電セラミック素子である。The piezoelectric ceramic composition according to the present invention is a piezoelectric ceramic composition comprising a main component represented by the general formula CaBi 4 Ti 4 O 15 , wherein at least W is represented by the general formula. A piezoelectric ceramic composition characterized by containing 0.5 mol or less (not including 0) with respect to 1 mol of Bi in the main component. In this case, the piezoelectric ceramic composition according to the present invention has, for example, the general formula CaBi 4
It consists of a main component represented by (Ti 1-y W y ) 4 O 15 (where 0 <y ≦ 0.5). In the piezoelectric ceramic composition according to the present invention, the bivalent metal element other than Ca is Bi, 1 mol
0.125 mol or less (not including 0) based on the total amount. In this case, the contained divalent metal element other than Ca is, for example, at least one of Mg, Sr, and Ba. Further, in the piezoelectric ceramic composition according to the present invention, the trivalent metal element other than Bi is Bi, 1 mol
May be contained in an amount of 0.075 mol or less (not including 0). In this case, the contained trivalent metal element other than Bi is, for example, La, Ce, Pr, Nd, Sm, G
It is at least one of d, Dy, Er, Yb, Sc and Y. Further, in the piezoelectric ceramic composition according to the present invention, manganese is 1.5% by weight in terms of MnCO 3.
The following (not including 0) may be contained. A piezoelectric ceramic element according to the present invention is a piezoelectric ceramic element including a piezoelectric ceramic made of the piezoelectric ceramic composition according to the present invention, and electrodes formed on the piezoelectric ceramic.
【０００６】この発明にかかる圧電磁器組成物におい
て、ＷをＢｉ、１ｍｏｌに対して０．５ｍｏｌ以下（０
を含まない）含有するとしたのは、これより多い場合に
は電気機械結合係数ｋｔの低下がみられ、実用的な電気
機械結合係数が得られないためである。また、この発明
は、主成分中にＭｇ、ＳｒおよびＢａなどの２価の金属
元素、または、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、
Ｄｙ、Ｅｒ、Ｙｂ、ＳｃおよびＹなどの３価の金属元素
を含有する圧電磁器組成物についても有効である。特
に、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｄｙ、Ｅ
ｒ、Ｙｂ、ＳｃおよびＹのうちの少なくとも１種をＢ
ｉ、１ｍｏｌに対して０．０７５ｍｏｌ以下（０を含ま
ない）含有する場合には、理由は不明であるが、−２０
℃から８０℃の共振周波数の温度変化率、すなわち、以
下に示す式で表されるｆｒＴＣが減少するため、１１０
０℃以下で焼成可能で実用に供しうる程度の電気機械結
合係数を有し、かつ、共振周波数の温度変化率ｆｒＴＣ
の小さい、たとえば圧電セラミック発振子などの圧電セ
ラミック素子などの材料として有用な圧電磁器組成物が
得られる。ここで、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇ
ｄ、Ｄｙ、Ｅｒ、Ｙｂ、ＳｃおよびＹのうちの少なくと
も１種をＢｉ、１ｍｏｌに対して０．０７５ｍｏｌ以下
（０を含まない）含有するとしたのは、これより多い場
合には上記元素を含まない場合に比べ電気機械結合係数
ｋｔの低下がみられ、これらを用いる効果がないためで
ある。 ｆｒＴＣ＝（ｆｒ（max ）−ｆｒ（min ））／（ｆｒ
（20℃）・１００） ｆｒ（max ）：−２０℃から８０℃の温度範囲において
最高の共振周波数 ｆｒ（min ）：−２０℃から８０℃の温度範囲において
最低の共振周波数 ｆｒ（20℃）：２０℃での共振周波数 さらに、我々は特願平１１−０３０３２２号においてＣ
ａＢｉ4 Ｔｉ4 Ｏ15を主成分とする圧電磁器組成物にマ
ンガンをＭｎＣＯ3 に換算して１．５重量％以下含有す
ることにより電気機械結合係数が向上することを明らか
にしたが、このような圧電磁器組成物においてもこの発
明は有効であり、１１００℃以下で焼成可能で実用に供
しうる程度の電気機械結合係数を有する圧電磁器の材料
として有用な圧電磁器組成物が得られる。In the piezoelectric ceramic composition according to the present invention, W is not more than 0.5 mol (0 mol
Is included) because if it is more than this, the electromechanical coupling coefficient kt decreases, and a practical electromechanical coupling coefficient cannot be obtained. Further, the present invention provides a divalent metal element such as Mg, Sr and Ba in the main component, or La, Ce, Pr, Nd, Sm, Gd,
It is also effective for piezoelectric ceramic compositions containing trivalent metal elements such as Dy, Er, Yb, Sc and Y. In particular, La, Ce, Pr, Nd, Sm, Gd, Dy, E
at least one of r, Yb, Sc and Y is B
When i is contained in an amount of 0.075 mol or less (not including 0) with respect to 1 mol, the reason is unknown, but -20
Since the temperature change rate of the resonance frequency from 80 ° C. to 80 ° C., that is, frTC expressed by the following equation is reduced, 110
It has an electromechanical coupling coefficient that can be practically used at 0 ° C. or less, and has a temperature change rate frTC of the resonance frequency.
Thus, a piezoelectric ceramic composition having a small value and useful as a material for a piezoelectric ceramic element such as a piezoelectric ceramic oscillator can be obtained. Here, La, Ce, Pr, Nd, Sm, G
The content of at least one of d, Dy, Er, Yb, Sc and Y is set to 0.075 mol or less (not including 0) based on 1 mol of Bi. This is because the electromechanical coupling coefficient kt is reduced as compared with the case where there is no effect, and there is no effect of using these. frTC = (fr (max) -fr (min)) / (fr
(20 ° C) · 100) fr (max): Highest resonance frequency in the temperature range from -20 ° C to 80 ° C fr (min): Lowest resonance frequency in the temperature range from -20 ° C to 80 ° C fr (20 ° C) : Resonance frequency at 20 ° C. Further, in Japanese Patent Application No. 11-030322,
It has been clarified that the electromechanical coupling coefficient is improved by containing 1.5% by weight or less of manganese in terms of MnCO 3 in a piezoelectric ceramic composition containing aBi 4 Ti 4 O 15 as a main component. The present invention is effective also in a piezoelectric ceramic composition, and a piezoelectric ceramic composition useful as a material of a piezoelectric ceramic having an electromechanical coupling coefficient that can be fired at 1100 ° C. or less and can be practically used is obtained.
【０００７】この発明の上述の目的、その他の目的、特
徴および利点は、図面を参照して行う以下の発明の実施
の形態の詳細な説明から一層明らかとなろう。The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments of the present invention with reference to the accompanying drawings.
【０００８】[0008]
【発明の実施の形態】（実施例）まず、出発原料とし
て、ＣａＣＯ3 、Ｂｉ2 Ｏ3 、ＴｉＯ2 、ＭｇＣＯ3 、
ＳｒＣＯ3 、ＢａＣＯ3 、Ｌａ2 Ｏ3 、Ｎｄ2 Ｏ3 、Ｓ
ｍ2 Ｏ3 、Ｙ2 Ｏ3 、ＷＯ 6 およびＭｎＣＯ3 を用意
し、これらを組成（Ｃａ1-x Ｍx ）Ｂｉ4 （Ｔｉ1-yＷ
y ）4 Ｏ15＋ｚ重量％ＭｎＣＯ3 （ＭはＭｇ、Ｓｒ、Ｂ
ａ、Ｌａ、Ｎｄ、Ｓｍ、Ｙのいずれか。０≦ｙ≦０．
６、０≦ｚ≦１．６。また、ＭがＭｇ、Ｓｒ、Ｂａのと
き０≦ｘ≦０．６、ＭがＬａ、Ｎｄ、Ｓｍ、Ｙのとき０
≦ｘ≦０．４。）となるように秤取して、ボールミルを
用いて約４時間湿式混合して、混合物を得た。得られた
混合物を乾燥した後、７００〜９００℃で仮焼して、仮
焼物を得た。それから、この仮焼物を粗粉砕した後、有
機バインダを適量加えてボールミルを用いて４時間湿式
粉砕し、４０メッシュのふるいを通して粒度調整を行っ
た。次に、これを１０００ｋｇ／ｃｍ2 の圧力で直径１
２．５ｍｍ、厚さ１ｍｍの円板に成型し、これを大気中
で１１００〜１１５０℃で焼成することによって、円板
状の磁器を得た。この磁器の表面（両主面）に、通常の
方法により銀ペーストを塗布し焼付けて銀電極を形成し
た後、１５０〜２００℃の絶縁オイル中で５〜１０ｋＶ
／ｍｍの直流電圧を１０〜３０分間印加して分極処理を
施し、圧電磁器（試料）を得た。そして、得られた試料
について、密度、共振周波数の温度変化率ｆｒＴＣおよ
び電気機械結合係数ｋｔを測定した。その結果を表１〜
表３に示す。なお、表１〜表３には、各試料の組成にお
けるＭの元素記号と、ｘ、ｙおよびｚの数値と、焼成温
度とも示す。また、表１〜表３において、試料 No.欄の
＊印はその試料がこの発明の範囲外であることを示す。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS (Example) First, as a starting material,
And CaCOThree, BiTwoOThree, TiOTwo, MgCOThree,
SrCOThree, BaCOThree, LaTwoOThree, NdTwoOThree, S
mTwoOThree, YTwoOThree, WO 6And MnCOThreePrepared
And these are composed (Ca1-xMx) BiFour(Ti1-yW
y)FourOFifteen+ Z wt% MnCOThree(M is Mg, Sr, B
any of a, La, Nd, Sm, and Y. 0 ≦ y ≦ 0.
6, 0 ≦ z ≦ 1.6. M is Mg, Sr, or Ba.
0 ≦ x ≦ 0.6, 0 when M is La, Nd, Sm, Y
≦ x ≦ 0.4. ) And weigh the ball mill.
The mixture was wet-mixed for about 4 hours to obtain a mixture. Got
After drying the mixture, it is calcined at 700 to 900 ° C.
I got a pottery. Then, after roughly crushing this calcined product,
4 hours wet using a ball mill after adding an appropriate amount of binder
Pulverize and adjust the particle size through a 40 mesh sieve
Was. Next, this is 1000 kg / cmTwoDiameter 1 at pressure
It is molded into a 2.5mm, 1mm thick disk, which is
Baking at 1100 to 1150 ° C with a disc
Porcelain was obtained. Normal surface (both main surfaces) of this porcelain
Apply silver paste and bake to form silver electrodes
After that, 5 to 10 kV in insulating oil at 150 to 200 ° C
/ Mm DC voltage for 10 to 30 minutes
Then, a piezoelectric ceramic (sample) was obtained. And the obtained sample
For the density, the temperature change rate frTC of the resonance frequency and
And the electromechanical coupling coefficient kt were measured. Table 1 shows the results.
It is shown in Table 3. Tables 1 to 3 show the composition of each sample.
Symbol of M, the numerical values of x, y and z, and the firing temperature
Also shown as degrees. In Tables 1 to 3, the sample No.
The asterisk indicates that the sample is outside the scope of the invention.
【０００９】[0009]
【表１】 [Table 1]
【００１０】[0010]
【表２】 [Table 2]
【００１１】[0011]
【表３】 [Table 3]
【００１２】表１〜表３において、上記の一般式中のｘ
の１／４すなわちｘ／４がＢｉ、１ｍｏｌに対するＭの
含有量（ｍｏｌ）に相当すること、また、ｙがＢｉ、１
ｍｏｌに対してのＷの含有量（ｍｏｌ）に相当すること
に注意されたい。In Tables 1 to 3, x in the above general formula
す な わ ち, ie, x / 4 corresponds to the content (mol) of Bi with respect to 1 mol of Bi, and y represents Bi, 1
Note that this corresponds to the W content (mol) relative to mol.
【００１３】表１〜表３から明らかなように、この発明
において上記の一般式中のｙの範囲を０＜ｙ≦０．５と
したのは、これ未満では１１００℃以下の焼成温度では
十分な焼結が行われず、分極が不可能なためであり、ま
た、これを超えると実用に供しうる程度の電気機械結合
係数ｋｔが得られないためである。また、この発明にお
いてＭが２価の金属元素であるＭｇ、ＳｒおよびＢａの
うちの少なくとも１種である場合に上記の一般式中のｘ
の１／４すなわちｘ／４の範囲を０≦ｘ／４≦０．１２
５としたのは、これを超えると、Ｍを含まない場合に比
べ、電気機械結合係数ｋｔが低下しており、Ｍを用いる
効果がないためである。さらに、この発明においてＭが
３価の金属元素であるＬａ、Ｎｄ、ＳｍおよびＹのうち
の少なくとも１種である場合に上記の一般式中のｘの１
／４すなわちｘ／４の範囲を０≦ｘ／４≦０．０７５と
したのは、これを超えると、Ｍを含まない場合に比べ、
電気機械結合係数ｋｔが低下しており、Ｍを用いる効果
がないためである。また、この発明においてマンガンの
添加量をＭｎＣＯ3 に換算して１．５重量％以下とした
のは、添加量がこれより多い場合には、マンガンを含ま
ない場合に比べ、電気機械結合係数ｋｔおよび共振周波
数の温度変化率ｆｒＴＣが低下しており、マンガンを用
いる効果がないためである。As is apparent from Tables 1 to 3, in the present invention, the range of y in the above general formula is set to 0 <y ≦ 0.5. This is because no sintering is performed and polarization is impossible, and if it exceeds this, an electromechanical coupling coefficient kt that can be practically used cannot be obtained. In the present invention, when M is at least one of Mg, Sr and Ba which are divalent metal elements, x in the above general formula
Is set to 0 ≦ x / 4 ≦ 0.12.
The reason for setting it to 5 is that if it exceeds this value, the electromechanical coupling coefficient kt is lower than in the case where M is not included, and there is no effect of using M. Further, in the present invention, when M is at least one of La, Nd, Sm and Y which are trivalent metal elements, when M in the above general formula is 1
/ 4, that is, the range of x / 4 is set to 0 ≦ x / 4 ≦ 0.075.
This is because the electromechanical coupling coefficient kt is reduced and there is no effect of using M. Further, in the present invention, the addition amount of manganese is set to 1.5% by weight or less in terms of MnCO 3 , when the addition amount is larger than this, the electromechanical coupling coefficient kt is smaller than when manganese is not included. Also, the temperature change rate frTC of the resonance frequency is reduced, and there is no effect of using manganese.
【００１４】一方、表１〜表３から明らかなように、こ
の発明の実施例にかかる各試料については、いずれも、
１１００℃以下の焼成温度で実用に供しうる程度の電気
機械結合係数ｋｔが得られていることがわかる。さら
に、表１〜表３から明らかなように、この発明の実施例
にかかる試料において、ＭがＬａ、Ｎｄ、ＳｍおよびＹ
のうちの少なくとも１種である場合、１１００℃以下の
焼成温度で実用に供しうる程度の電気機械結合係数ｋｔ
を有し、かつ、共振周波数の温度変化率ｆｒＴＣが小さ
い圧電磁器の材料として有用な圧電磁器組成物が得られ
ることが明らかである。また、ＭがＮｄ、Ｙのうち少な
くとも１種である場合には、共振周波数の温度変化率ｆ
ｒＴＣが特に小さい圧電磁器組成物が得られることがわ
かる。On the other hand, as is clear from Tables 1 to 3, each of the samples according to the embodiments of the present invention
It can be seen that an electromechanical coupling coefficient kt that can be practically used is obtained at a firing temperature of 1100 ° C. or less. Further, as is apparent from Tables 1 to 3, in the samples according to the examples of the present invention, M is La, Nd, Sm and Y.
When at least one of the above is used, the electromechanical coupling coefficient kt is such that it can be practically used at a firing temperature of 1100 ° C. or less.
It is clear that a piezoelectric ceramic composition useful as a material for a piezoelectric ceramic having a small temperature change rate frTC of the resonance frequency and having a resonance frequency is obtained. When M is at least one of Nd and Y, the temperature change rate f of the resonance frequency f
It can be seen that a piezoelectric ceramic composition having particularly small rTC can be obtained.
【００１５】なお、この発明にかかる圧電磁器組成物は
上記の実施例の組成に限定されるものではなく、発明の
要旨の範囲内であれば有効である。この発明にかかる一
般式ＣａＢｉ4 Ｔｉ4 Ｏ15を主成分とする圧電磁器組成
物は、基本的に上記のような組成を有していればよく、
構成元素の多少のモル比のずれがあっても構わない。Incidentally, the piezoelectric ceramic composition according to the present invention is not limited to the composition of the above-mentioned embodiment, but is effective within the scope of the invention. The piezoelectric ceramic composition having the general formula CaBi 4 Ti 4 O 15 as a main component according to the present invention basically has only to have the above composition,
There may be some deviation in the molar ratio of the constituent elements.
【００１６】図１はこの発明にかかる圧電セラミック振
動子の一例を示す斜視図であり、図２はその断面図解図
である。図１および図２に示す圧電セラミック振動子１
０は、たとえば直方体状の圧電磁器１２を含む。圧電磁
器１２は、２枚の圧電磁器層１２ａおよび１２ｂを含
む。これらの圧電磁器層１２ａおよび１２ｂは、上述の
この発明にかかる圧電磁器組成物からなり、積層されか
つ一体的に形成される。また、これらの圧電磁器層１２
ａおよび１２ｂは、図２の矢印で示すように、同じ厚み
方向に分極されている。FIG. 1 is a perspective view showing an example of a piezoelectric ceramic vibrator according to the present invention, and FIG. 2 is a schematic sectional view thereof. Piezoelectric ceramic vibrator 1 shown in FIGS. 1 and 2
0 includes, for example, a rectangular parallelepiped piezoelectric ceramic 12. The piezoelectric ceramic 12 includes two piezoelectric ceramic layers 12a and 12b. These piezoelectric ceramic layers 12a and 12b are made of the above-described piezoelectric ceramic composition according to the present invention, and are laminated and integrally formed. In addition, these piezoelectric ceramic layers 12
a and 12b are polarized in the same thickness direction, as indicated by the arrows in FIG.
【００１７】圧電磁器層１２ａおよび１２ｂの間には、
その中央にたとえば円形の振動電極１４ａが形成され、
その振動電極１４ａから圧電磁器１２の一端面にわたっ
てたとえばＴ字形の引出電極１６ａが形成される。ま
た、圧電磁器層１２ａの表面には、その中央にたとえば
円形の振動電極１４ｂが形成され、その振動電極１４ｂ
から圧電磁器１２の他端面にわたってたとえばＴ字形の
引出電極１６ｂが形成される。さらに、圧電磁器層１２
ｂの表面には、その中央にたとえば円形の振動電極１４
ｃが形成され、その振動電極１４ｃから圧電磁器１２の
他端面にわたってたとえはＴ字形の引出電極１６ｃが形
成される。Between the piezoelectric ceramic layers 12a and 12b,
At its center, for example, a circular vibration electrode 14a is formed,
For example, a T-shaped extraction electrode 16a is formed from the vibration electrode 14a to one end surface of the piezoelectric ceramic 12. On the surface of the piezoelectric ceramic layer 12a, for example, a circular vibrating electrode 14b is formed at the center thereof.
From the other end of the piezoelectric ceramic 12, a T-shaped extraction electrode 16b is formed, for example. Further, the piezoelectric ceramic layer 12
b, for example, a circular vibrating electrode 14
Thus, a T-shaped extraction electrode 16c is formed from the vibrating electrode 14c to the other end surface of the piezoelectric ceramic 12.
【００１８】そして、引出電極１６ａにはリード線１８
ａを介して一方の外部電極２０ａが接続され、引出電極
１６ｂおよび１６ｃには別のリード線１８ｂを介して他
方の外部電極２０ｂが接続される。The lead wire 18 is connected to the extraction electrode 16a.
One external electrode 20a is connected via a, and the other external electrode 20b is connected to the extraction electrodes 16b and 16c via another lead wire 18b.
【００１９】なお、この発明は、上述の圧電セラミック
振動子１０以外の圧電セラミック振動子、圧電セラミッ
クフィルタおよび圧電セラミック発振子などの他の圧電
セラミック素子にも適用される。The present invention is applicable to other piezoelectric ceramic elements such as a piezoelectric ceramic vibrator other than the above-described piezoelectric ceramic vibrator 10, a piezoelectric ceramic filter, and a piezoelectric ceramic vibrator.
【００２０】[0020]
【発明の効果】この発明によれば、ＣａＢｉ4 Ｔｉ4 Ｏ
15を主成分とする圧電磁器組成物の焼成が可能な温度を
低下させ、１１００℃以下の焼成温度で実用に供しうる
程度の電気機械結合係数ｋｔを示す圧電セラミックフィ
ルタ、圧電セラミック発振子および圧電セラミック振動
子などの圧電セラミック素子などの材料として有用な圧
電磁器組成物およびそれを用いた圧電セラミック素子を
得ることができる。According to the present invention, CaBi 4 Ti 4 O
A piezoelectric ceramic filter, a piezoelectric ceramic oscillator, and a piezoelectric ceramic exhibiting an electromechanical coupling coefficient kt that is low enough to be practically usable at a firing temperature of 1100 ° C. or less by reducing the firing temperature of the piezoelectric ceramic composition containing 15 as a main component. A piezoelectric ceramic composition useful as a material for a piezoelectric ceramic element such as a ceramic vibrator and a piezoelectric ceramic element using the same can be obtained.
【図１】この発明にかかる圧電セラミック振動子の一例
を示す斜視図である。FIG. 1 is a perspective view showing an example of a piezoelectric ceramic vibrator according to the present invention.
【図２】図１に示す圧電セラミック振動子の断面図解図
である。FIG. 2 is an illustrative sectional view of the piezoelectric ceramic vibrator shown in FIG.
１０ 圧電セラミック振動子 １２ 圧電磁器 １２ａ、１２ｂ 圧電磁器層 １４ａ、１４ｂ、１４ｃ 振動電極 １６ａ、１６ｂ、１６ｃ 引出電極 １８ａ、１８ｂ リード線 ２０ａ、２０ｂ 外部端子 DESCRIPTION OF SYMBOLS 10 Piezoelectric ceramic vibrator 12 Piezoelectric ceramic 12a, 12b Piezoelectric ceramic layer 14a, 14b, 14c Vibrating electrode 16a, 16b, 16c Leading electrode 18a, 18b Lead wire 20a, 20b External terminal
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安藤 陽 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 (72)発明者 林 宏一 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 Ｆターム(参考） 4G031 AA02 AA03 AA04 AA05 AA06 AA07 AA08 AA09 AA11 AA18 AA24 AA27 AA35 AA37 BA10 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yo Youto 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto Inside Murata Manufacturing Co., Ltd. (72) Koichi Hayashi 2-26-10 Tenjin, Nagaokakyo-shi, Kyoto Stock Company F-term in Murata Manufacturing (reference) 4G031 AA02 AA03 AA04 AA05 AA06 AA07 AA08 AA09 AA11 AA18 AA24 AA27 AA35 AA37 BA10
Claims (8)
主成分からなる圧電磁器組成物において、少なくともＷ
を前記一般式で表される主成分中のＢｉ、１ｍｏｌに対
して０．５ｍｏｌ以下（０を含まない）含有することを
特徴とする、圧電磁器組成物。1. A piezoelectric ceramic composition comprising a main component represented by the general formula CaBi 4 Ti 4 O 15 , wherein at least W
Is contained in 0.5 mol or less (excluding 0) with respect to 1 mol of Bi in the main component represented by the above general formula.
15（ただし、０＜ｙ≦０．５）で表される主成分からな
ることを特徴とする、請求項１に記載の圧電磁器組成
物。2. The general formula CaBi 4 (Ti 1-y W y ) 4 O
15. The piezoelectric ceramic composition according to claim 1, comprising a main component represented by 15 (where 0 <y ≦ 0.5).
ｏｌに対して０．１２５ｍｏｌ以下（０を含まない）含
有することを特徴とする、請求項１または請求項２に記
載の圧電磁器組成物。3. A bivalent metal element other than Ca is Bi, 1 m
The piezoelectric ceramic composition according to claim 1, wherein the composition contains 0.125 mol or less (not including 0) with respect to ol.
Ｍｇ、ＳｒおよびＢａのうちの少なくとも１種であるこ
とを特徴とする、請求項３に記載の圧電磁器組成物。4. The piezoelectric ceramic composition according to claim 3, wherein the divalent metal element other than Ca contained is at least one of Mg, Sr, and Ba.
ｏｌに対して０．０７５ｍｏｌ以下（０を含まない）含
有することを特徴とする、請求項１または請求項２に記
載の圧電磁器組成物。5. The method according to claim 1, wherein the trivalent metal element other than Bi is Bi, 1 m
The piezoelectric ceramic composition according to claim 1, wherein the piezoelectric ceramic composition contains 0.075 mol or less (not including 0) with respect to ol.
Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｄｙ、Ｅｒ、Ｙ
ｂ、ＳｃおよびＹのうちの少なくとも１種であることを
特徴とする、請求項５に記載の圧電磁器組成物。6. The trivalent metal element other than Bi contained is La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Y.
The piezoelectric ceramic composition according to claim 5, wherein the piezoelectric ceramic composition is at least one of b, Sc, and Y.
重量％以下（０を含まない）含有することを特徴とす
る、請求項１ないし請求項６のいずれかに記載の圧電磁
器組成物。7. Manganese is converted to MnCO 3 by 1.5
The piezoelectric ceramic composition according to any one of claims 1 to 6, wherein the composition contains not more than 0% by weight (not including 0).
載の圧電磁器組成物からなる圧電磁器、および前記圧電
磁器に形成される電極を含む、圧電セラミック素子。8. A piezoelectric ceramic element comprising a piezoelectric ceramic comprising the piezoelectric ceramic composition according to claim 1, and an electrode formed on the piezoelectric ceramic.
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|---|---|---|---|
| JP2000161832A JP3788198B2 (en) | 1999-08-26 | 2000-05-31 | Piezoelectric ceramic composition and piezoelectric ceramic element using the same |
| TW089115657A TW469447B (en) | 1999-08-26 | 2000-08-04 | Piezoelectric ceramic composition and ceramic piezoelectric device employing the composition |
| US09/643,785 US6372152B1 (en) | 1999-08-26 | 2000-08-22 | Piezoelectric ceramic composition and ceramic piezoelectric device employing the composition |
| DE10041307A DE10041307B4 (en) | 1999-08-26 | 2000-08-23 | Piezoelectric ceramic composition and its use |
| KR10-2000-0049523A KR100379202B1 (en) | 1999-08-26 | 2000-08-25 | Piezoelectric Ceramic Composition and Ceramic Piezoelectric Device Employing the Composition |
| CNB001262203A CN1219297C (en) | 1999-08-26 | 2000-08-25 | Piezoelectric ceramics composition and piezoelectric device using same |
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| JP24014699 | 1999-08-26 | ||
| JP2000161832A JP3788198B2 (en) | 1999-08-26 | 2000-05-31 | Piezoelectric ceramic composition and piezoelectric ceramic element using the same |
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| JP3788198B2 JP3788198B2 (en) | 2006-06-21 |
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|---|---|
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| JP (1) | JP3788198B2 (en) |
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| CN100371293C (en) * | 2004-03-30 | 2008-02-27 | 中国科学院上海硅酸盐研究所 | Technique for fabricating laminar piezoelectric ceramics of texturing bismuth through silkscreen printing with no template |
| CN103102154A (en) * | 2013-02-03 | 2013-05-15 | 北京工业大学 | Bi0.5Na0.5TiO3-BaTiO3-BiMg0.5Ti0.5O3 lead-free piezoelectric ceramic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH1130322A (en) * | 1997-07-10 | 1999-02-02 | Daihatsu Motor Co Ltd | Hydraulic control device de for automatic transmission |
| JP3931513B2 (en) * | 1999-02-08 | 2007-06-20 | 株式会社村田製作所 | Piezoelectric ceramic composition and piezoelectric ceramic element using the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371293C (en) * | 2004-03-30 | 2008-02-27 | 中国科学院上海硅酸盐研究所 | Technique for fabricating laminar piezoelectric ceramics of texturing bismuth through silkscreen printing with no template |
| JP2006169032A (en) * | 2004-12-15 | 2006-06-29 | Ngk Spark Plug Co Ltd | Piezoelectric ceramic composition and piezoelectric element |
| CN103102154A (en) * | 2013-02-03 | 2013-05-15 | 北京工业大学 | Bi0.5Na0.5TiO3-BaTiO3-BiMg0.5Ti0.5O3 lead-free piezoelectric ceramic material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1219297C (en) | 2005-09-14 |
| US6372152B1 (en) | 2002-04-16 |
| TW469447B (en) | 2001-12-21 |
| CN1286477A (en) | 2001-03-07 |
| KR100379202B1 (en) | 2003-04-08 |
| DE10041307B4 (en) | 2005-03-17 |
| JP3788198B2 (en) | 2006-06-21 |
| DE10041307A1 (en) | 2001-03-29 |
| KR20010050207A (en) | 2001-06-15 |
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